CN1031416C - 镁基储氢合金电极及其制备方法 - Google Patents

镁基储氢合金电极及其制备方法 Download PDF

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CN1031416C
CN1031416C CN92100030A CN92100030A CN1031416C CN 1031416 C CN1031416 C CN 1031416C CN 92100030 A CN92100030 A CN 92100030A CN 92100030 A CN92100030 A CN 92100030A CN 1031416 C CN1031416 C CN 1031416C
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magnesium
alloy electrode
magnuminium
hydrogen
alloy
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CN1064175A (zh
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张允什
宋德瑛
陈有孝
陈军
汪根时
袁华堂
周作祥
曹学军
藏弢石
张大昕
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Nankai University
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Priority to EP92310181A priority patent/EP0550958B1/en
Priority to CA002085034A priority patent/CA2085034A1/en
Priority to JP5017065A priority patent/JPH0676817A/ja
Priority to US08/219,752 priority patent/US5576118A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S420/00—Alloys or metallic compositions
    • Y10S420/90—Hydrogen storage

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
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Abstract

本发明属于基于镁合金的活性物质材料制成的储氢合金电极。该电极的镁基合金材料经过包覆和活化处理，在常温和常压下就有良好的吸放氢的能力，用它制成的电极组装的碱蓄电池有高的重量比能量值和充放电容量，可以应用于大型电器设备，尤其是用在电动车辆上。

Description

镁基储氢合金电极及其制备方法
本发明属于基于镁合金的活性物质材料制成的储氢合金电极。
据文献(松本功，新型储氢合金蓄电池，国外稀土情报，1990，3)介绍，目前开发出的储氢合金活性物质材料有稀土系(LaNi5等)，钛系(TiNi等)，锆等(ZrMn2等)，钙系(CaNi5等)和镁系(Mg2Ni等)，其中研究最多并逐渐被应用于碱蓄电池(主要是集中在便携式设备电源用的圆筒密封电池)中的是稀土系和钛系合金，其次是锆系和钙系合金，至于镁系合金的研究报道几乎绝无仅有。
然而，现今大型电器设备，尤其是电动车辆对碱蓄电池的性能提出了更高的要求，其中主要技术指标之一是高的重量比能量。由于稀土系合金和钛系合金元素本身重量大，从根本上限制了用它们为材料制成的电极组装成的碱蓄电池的重量比能量值的提高，再加稀土系合金、钛系合金和锆系合金的价格昂贵，因此限制了它们在大型电器设备用的碱蓄电池中应用的发展，而在这一方面应用最理想的储氢合金非镁系合金莫属了。但是由于氢在镁基中相对稳定，只能在高压和高温下才可能吸收和放出氢，目前开发的镁基合金要在3～10个大气压的高压下才能吸氢，300℃的高温下才能放氢(Seiler，S.；Sehlapbach，L.；von Waldkieh，Th.；J.Less-Common Met.1980，73，193；Nomura，K.；Akiba，E.；Int.J.Hydrogen Energy，1981，6，295)。这样的镁基合金在常态下是无法应用的。
本发明的任务是提出一种重量比能量值高的，具有良好催化活性的并且在常温常压下可充分地吸放氢的镁基储氢合金电极。
本发明的任务是这样实现的：用在化学组成为Mg2－xNi1－yAyBx(其中A＝Sn、Sb、Bi，B＝Li、Na、K、Al，0.1≤x≤1.5，0.1≤y≤0.5)的镁基合金粉未表面包覆一层厚度为微米级的Ni、Cr、P金属化合物，和经过活化处理使在镁基合金基体与Ni、Cr、P金属化合物之间形成另一种与前两者有不同组成结构的合金相的活性物质材料制成镁基储氢合金电极。
本发明化学组成为Mg2－xNi1-yAyBx的镁基合金粉未是以真空冶炼方法炼出，用振磨机磨成50μm～38μm而制得的。
本发明的镁基合金粉未上包覆的一层微米级厚度的Ni、 Cr、P金属化合物是以化学镀的方式沉积在镁基合金粉未表面上的。
本发明提出的活化处理方法是先用烃类有机物浸泡镁基合金粉未，再进行化学镀沉积上Ni、Cr、P金属化合物，最后放入真空炉中在60～100℃下处理10～20小时。
将经过包覆和活化处理的镁基合金粉未按一般的制作电极的工艺流程制成镁基储氢合金电极。
以本发明制得的经过表面活化和包覆处理的镁基储氢合金电极由于改变了镁基合金的吸氢结构，使氢在镁基合金中的稳定性下降，因此在常温常压下就能很好地吸入氢，并具有良好的催化活性。用这种镁基合金电极组装的碱蓄电池有较高的重量比能量值和充放电容量，而且价格便宜，可以广泛应用于大型电器设备，特别是用在电动车辆上。
实施例
在真空感应炉中冶炼出化学组成为Mg1.8Ni0.8Sn0.2A10.2的镁基合金。将该合金用粉碎机粉碎后用振磨机磨成50μm～38μm的粉未，然后放入烷基有机物中浸泡10分钟。取出浸泡过的镁基合金粉未，用化学镀方法在其表面沉积一层微米级厚度的Ni、Cr、P金属化合物。将包覆有Ni、Cr、P金属化合物的镁基合金粉未放进真空炉中，在80℃下保温处理12小时。取经包覆和活化处理过的镁基合金粉未1克，按一般工艺制成镁基储氢合金电极。以此镁基储氢合金电极为负极，氧化镍为正极，用Hg/HgO为参比电极测出其电化学容量和重量比能量值。表1中列出了本镁基合金电极与稀土系合金电极和钛系合金电极的电化学容量和重量比能量值的对比数据。
表1.三种储氢合金电极电化学容量和重量比能量值的对比数据
    储氢合金     放电倍率     0.1c  0.2c
LaNi3.8Co0.5Mn0.4Al0.3 电化学容量(mAh/g)     290  284
重量比能量(Wh/Kg)     55.2  54.8
TiNi 电化学容量(mAh/g)     280  272
重量比能量(Wh/Kg)     52  50
Mg1.8Ni0.8Sn0.2Al0.2 电化学容量(mAh/g)     240  236
重量比能量(Wh/Kg)     66.3  66.0

Claims (2)

1.一种储氢合金电极，由镁系合金组成，其特征在于：它的化学组成为Mg2-xNi1-ySnyAlx，0.1≤x≤1.5，0.1≤y≤0.5，在镁基合金粉未的表面包覆有一层微米级厚度的Ni、Cr、P金属化合物。
2.一种制造权利要求1所述的储氢合金电极的方法，其特征在于：将在真空感应炉中冶炼出后磨成50μm～38μm的镁基合金粉未放入脂肪族烃及其衍生物或芳香烃及其衍生物中浸泡，进行活化处理，然后取出用化学镀方法在其表面包覆一层微米级厚度的Ni、Cr、P金属化合物，再放进真空炉中在60～100℃下处理10～20小时，将由此处理过的镁基合金粉未接一般工艺流程制成镁基储氢合金电极。
CN92100030A 1992-01-08 1992-01-08 镁基储氢合金电极及其制备方法 Expired - Fee Related CN1031416C (zh)

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Application Number Priority Date Filing Date Title
CN92100030A CN1031416C (zh) 1992-01-08 1992-01-08 镁基储氢合金电极及其制备方法
DE69202237T DE69202237T2 (de) 1992-01-08 1992-11-06 Elektrode aus Wasserstoff speichernder, auf Magnesium basierender Legierung.
EP92310181A EP0550958B1 (en) 1992-01-08 1992-11-06 Magnesium-based hydrogen storage alloy electrode
CA002085034A CA2085034A1 (en) 1992-01-08 1992-12-10 Magnesium based hydrogen storage alloy electrode
JP5017065A JPH0676817A (ja) 1992-01-08 1993-01-07 マグネシウム系水素貯蔵合金
US08/219,752 US5576118A (en) 1992-01-08 1994-03-29 Magnesium based hydrogen storage alloy electrode

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CA2085034A1 (en) 1993-07-09
JPH0676817A (ja) 1994-03-18
CN1064175A (zh) 1992-09-02
EP0550958A1 (en) 1993-07-14
EP0550958B1 (en) 1995-04-26
DE69202237T2 (de) 1995-08-31
US5576118A (en) 1996-11-19

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